CN110400926B - Nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material and preparation method thereof - Google Patents
Nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007772 electrode material Substances 0.000 title claims abstract description 44
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000009826 distribution Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 229910052573 porcelain Inorganic materials 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims description 3
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims 3
- 239000000463 material Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000011669 selenium Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000013384 organic framework Substances 0.000 abstract description 2
- 229910052711 selenium Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition metal selenide Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229960001471 sodium selenite Drugs 0.000 description 2
- 235000015921 sodium selenite Nutrition 0.000 description 2
- 239000011781 sodium selenite Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229940091258 selenium supplement Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt double-metal selenide electrode material and a preparation method thereof, belonging to the field of preparation of electrode materials for lithium ion batteries. The preparation method comprises the following steps: preparing a nickel-cobalt bimetallic organic framework compound by taking nickel nitrate and cobalt nitrate as metal sources and trimesic acid as an organic ligand by a solvothermal method; putting the prepared nickel-cobalt bimetallic precursor and melamine into a 450 ℃ tubular furnace together to calcine for 2 h to finish the carbonization and nitrogen doping processes, thereby obtaining a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance; and (3) taking selenium powder as a selenium source, and converting the nitrogen-doped carbon-coated nickel-cobalt double-metal simple substance obtained after calcination into a nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material. Has higher specific capacitance, excellent rate capability and cycling stability.
Description
Technical Field
The invention belongs to the field of preparation of electrode materials for lithium ion batteries, and particularly relates to a nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt double-metal selenide electrode material and a preparation method thereof.
Background
A lithium ion battery is an electrochemical energy storage device that relies on the process of lithium ion intercalation and deintercalation for charge storage. It has the advantages of high specific energy, light weight, environmental protection, no pollution, small self-discharge, no memory effect, long service life and the like, thereby being widely applied to various aspects of life. Theoretically, lithium ions can be infinitely inserted into and extracted from the positive and negative electrode materials, but in practice, the lithium ion insertion and extraction process damages the microstructure of the electrode material, thereby causing problems of poor cycle performance and short service life of the battery, and therefore, the search for a battery electrode material with high performance is urgent. The transition metal selenide has high theoretical specific capacity, good conductivity and cycling stability, and does not generate alloying reaction to generate larger volume expansion in the process of lithium ion intercalation and deintercalation, thereby being a lithium ion battery electrode material with wide prospect.
However, the energy storage performance of the transition metal selenide electrode material is severely restricted by the factor of poor conductivity, so the nitrogen-doped carbon-coated two-phase cross distribution type nickel-cobalt double-metal selenide electrode material is prepared, and the electrochemical energy storage performance of the transition metal selenide is improved by utilizing the conductivity of the nitrogen-doped carbon material and the defects at the phase boundary of the two phases.
Disclosure of Invention
The invention aims to provide a nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material and a preparation method thereof. In order to further improve the electrochemical performance of the two-phase staggered nickel-cobalt double-metal selenide, in the calcining process, organic ligand trimesic acid is carbonized to form carbon, and nitrogen elements in melamine are doped into the carbon formed by the organic ligand, so that the conductivity and defects of an electrode material are improved, and the electrochemical performance is improved. The prepared electrode material is characterized in that nitrogen-doped carbon is coated outside two-phase staggered distribution type nickel-cobalt double-metal selenide particles with uniform sizes in the microscopic appearance, and the electrode material has high specific capacitance, excellent rate capability and cycle stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped carbon-coated two-phase nickel-cobalt double-metal selenide electrode material in a staggered distribution mode comprises the following steps:
(1) adding quantitative nickel nitrate, cobalt nitrate, polyvinylpyrrolidone and trimesic acid into N, N-dimethylformamide, transferring the mixed solution into a reaction kettle after ultrasonic full dissolution, placing the reaction kettle into a forced air drying oven for solvothermal reaction, then carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the mixed solution is naturally cooled to room temperature, and finally drying the washed product to obtain the nickel-cobalt bimetallic organic framework compound;
(2) respectively paving a quantitative centrifugal drying product obtained in the step (1) and a quantitative melamine in two porcelain boats, then placing the porcelain boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping, and finally naturally cooling the porcelain boats to room temperature to obtain a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance;
(3) and (3) adding a certain amount of the product obtained in the step (2) and a certain amount of selenium powder into a hydrazine hydrate solution, transferring the hydrazine hydrate solution into a reaction kettle, placing the reaction kettle into an air-blast drying oven for solvothermal reaction, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the reaction kettle is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material.
The nickel-cobalt double-metal selenide electrode material prepared by the invention has uniform particle size, and nitrogen-doped carbon is coated outside the particles.
The invention has the following remarkable advantages:
(1) the invention takes selenium powder as a selenium source, selenization is carried out by adopting a solvothermal mode, and the nickel-cobalt double-metal selenide with two phases alternately distributed is formed in the selenization process.
(2) During the calcination process, the organic ligand trimesic acid is carbonized to form carbon, and nitrogen elements in the melamine can be doped into the carbon formed by the organic ligand to improve the conductivity of the electrode material.
(3) The electrochemical energy storage performance of the transition metal selenide is improved by utilizing the conductivity of the nitrogen-doped carbon material and the defects at the phase boundary of two phases, the prepared electrode material has the capacity of 1411 mAh/g under the current density of 100 mA/g, the initial coulombic efficiency is 68.91%, the capacity of 870 mAh/g is still maintained after 100 cycles of cyclic charge and discharge, and the prepared electrode material has higher capacity and excellent cyclic stability compared with the single-phase metal selenide.
Drawings
FIG. 1 is an XRD diffraction pattern of the nitrogen-doped carbon-coated two-phase cross-distributed NiCo bimetallic selenide electrode material prepared in example 1, and it can be seen from the XRD diffraction pattern that NiSe is a component of the prepared NiCo bimetallic selenide2And CoSe2Two phases are formed;
fig. 2 is a scanning electron microscope image of the nitrogen-doped carbon-coated two-phase staggered nickel-cobalt bimetallic selenide electrode material prepared in example 1, and it can be seen from the image that the carbon-coated nickel-cobalt bimetallic selenide has a uniform particle size;
fig. 3 is an EDS diagram of the nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt dual metal selenide electrode material prepared in example 1;
fig. 4 is a high resolution diagram of the transmission electrode of the nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt double-metal selenide electrode material prepared in example 1, from which it can be seen that cobalt selenide and nickel selenide are alternately distributed, so that a large number of phase boundaries exist;
fig. 5 is a cycle curve diagram of the nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt dual-metal selenide electrode material prepared in example 1;
fig. 6 is a scanning electron microscope image of the nitrogen-doped carbon-coated single-phase distributed nickel-cobalt bimetallic selenide electrode material prepared in example 3, from which it can be seen that the carbon-coated single-phase distributed nickel-cobalt bimetallic selenide has a similar size radius and a regular sphere shape;
FIG. 7 is the XRD diffraction pattern of the nitrogen-doped carbon-coated single-phase distributed Ni-Co bimetallic selenide electrode material prepared in example 3, and it can be seen from the XRD diffraction pattern that the Ni-Co bimetallic selenide prepared is made of NiCo2Se4A phase composition;
fig. 8 is a cycle plot of the nitrogen-doped carbon-coated single-phase distributed nickel-cobalt duplex metal selenide electrode material prepared in example 3.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of a nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt double-metal selenide electrode material comprises the following specific steps:
(1) weighing 232.4 mg of nickel nitrate, 232.4 mg of cobalt nitrate, 1 g of polyvinylpyrrolidone and 150 mg of trimesic acid, adding the nickel nitrate, the 232.4 mg of cobalt nitrate, the polyvinylpyrrolidone and the trimesic acid into 30 mL of N, N-dimethylformamide, carrying out ultrasonic full dissolution, transferring the mixed solution into a reaction kettle, placing the reaction kettle into a 150 ℃ forced air drying oven for carrying out solvent thermal reaction for 6 hours, carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the mixed solution is naturally cooled to room temperature, and finally drying the washed product;
(2) weighing 100 mg of the centrifugally dried product obtained in the step (1) and 200 mg of melamine, respectively paving the product and the melamine in two porcelain boats, then placing the porcelain boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping treatment at 450 ℃ for 2 h, and finally obtaining a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance after the porcelain boats are naturally cooled to room temperature;
(3) and (3) weighing 30 mg of the product obtained in the step (2) and 158 mg of selenium powder, adding the product and 158 mg of selenium powder into 0.3 mol/L hydrazine hydrate solution, transferring the solution into a reaction kettle, placing the reaction kettle into a blast drying oven at 200 ℃ for solvothermal reaction for 6 hours, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the solution is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material.
Example 2
A preparation method of a nitrogen-doped carbon-coated two-phase cross-distributed nickel-cobalt double-metal selenide electrode material comprises the following specific steps:
(1) weighing 155 mg of nickel nitrate, 320 mg of cobalt nitrate, 1 g of polyvinylpyrrolidone and 150 mg of trimesic acid, adding the nickel nitrate, the 320 mg of cobalt nitrate, the polyvinylpyrrolidone and the trimesic acid into 30 mL of N, N-dimethylformamide, carrying out ultrasonic full dissolution, transferring the mixed solution into a reaction kettle, placing the reaction kettle into a 150 ℃ forced air drying oven for carrying out solvent thermal reaction for 6 hours, carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the mixture is naturally cooled to room temperature, and finally drying the washed product;
(2) weighing 100 mg of the centrifugally dried product obtained in the step (1) and 200 mg of melamine, respectively paving the product and the melamine in two porcelain boats, then placing the porcelain boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping treatment at 450 ℃ for 2 h, and finally obtaining a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance after the porcelain boats are naturally cooled to room temperature;
(3) and (3) weighing 40 mg of the product obtained in the step (2) and 150 mg of selenium powder, adding the product and 150 mg of selenium powder into 0.3 mol/L hydrazine hydrate solution, transferring the solution into a reaction kettle, placing the reaction kettle into a blast drying oven at 200 ℃ for solvothermal reaction for 6 hours, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the solution is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material.
Example 3
A preparation method of a nitrogen-doped carbon-coated single-phase distributed nickel-cobalt double-metal selenide electrode material comprises the following specific steps:
(1) weighing 155 mg of nickel nitrate, 320 mg of cobalt nitrate, 1 g of polyvinylpyrrolidone and 150 mg of trimesic acid, adding the nickel nitrate, the 320 mg of cobalt nitrate, the polyvinylpyrrolidone and the trimesic acid into 30 mL of N, N-dimethylformamide, carrying out ultrasonic full dissolution, transferring the mixed solution into a reaction kettle, placing the reaction kettle into a 150 ℃ forced air drying oven for carrying out solvent thermal reaction for 6 hours, carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the mixture is naturally cooled to room temperature, and finally drying the washed product;
(2) weighing 100 mg of the centrifugally dried product obtained in the step (1) and 200 mg of melamine, respectively paving the product and the melamine in two porcelain boats, then placing the porcelain boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping treatment at 450 ℃ for 2 h, and finally obtaining a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance after the porcelain boats are naturally cooled to room temperature;
(3) and (3) weighing 40 mg of the product obtained in the step (2) and 100 mg of sodium selenite, adding the product and 100 mg of sodium selenite into 0.3 mol/L hydrazine hydrate solution, transferring the product into a reaction kettle, placing the reaction kettle into a 140 ℃ forced air drying oven for carrying out solvothermal reaction for 6 h, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the product is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated single-phase distributed nickel-cobalt double-metal selenide electrode material.
Example 4
(1) The nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material prepared by the method, acetylene black (a conductive agent) and polyvinylidene fluoride (PVDF, a binder) are added and mixed according to the mass ratio of 7:2:1, then the mixture is uniformly coated on copper foil and assembled into a button battery in a glove box, the button battery is measured to have the capacity of 1411 mAh/g under the current density of 100 mA/g, the initial coulombic efficiency is 68.91%, and the capacity of 870 mAh/g can be still maintained after 100 cycles of cyclic charge and discharge.
(2) The nitrogen-doped carbon-coated single-phase distributed nickel-cobalt double-metal selenide electrode material prepared by the method, acetylene black (a conductive agent) and polyvinylidene fluoride (PVDF, a binder) are added and mixed according to the mass ratio of 7:2:1, then the mixture is uniformly coated on copper foil and assembled into a button battery in a glove box, the button battery is measured to have the capacity of 750 mAh/g under the current density of 100 mA/g, the initial coulombic efficiency is 65%, the capacity of 580 mAh/g is maintained after 100 cycles of cyclic charge and discharge, and the cyclic stability is poorer than that of the nitrogen-doped carbon-coated two-phase staggered distributed nickel-cobalt double-metal selenide.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. A preparation method of a nitrogen-doped carbon-coated two-phase nickel-cobalt double-metal selenide electrode material in a staggered distribution mode is characterized by comprising the following steps of: the method comprises the following steps:
(1) adding quantitative nickel nitrate, cobalt nitrate, polyvinylpyrrolidone and trimesic acid into N, N-dimethylformamide, transferring the mixed solution into a reaction kettle after ultrasonic full dissolution, placing the reaction kettle into a forced air drying oven for solvothermal reaction, then carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the mixed solution is naturally cooled to room temperature, and finally drying the washed product;
(2) respectively paving a quantitative centrifugal drying product obtained in the step (1) and a quantitative melamine in two porcelain boats, then placing the porcelain boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping, and finally naturally cooling the porcelain boats to room temperature to obtain a nitrogen-doped carbon-coated nickel-cobalt bimetallic simple substance;
(3) and (3) adding a certain amount of the product obtained in the step (2) and a certain amount of selenium powder into a hydrazine hydrate solution, transferring the hydrazine hydrate solution into a reaction kettle, placing the reaction kettle into an air-blast drying oven for solvothermal reaction, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the reaction kettle is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material.
2. The method of claim 1, wherein: the method comprises the following specific steps:
(1) weighing 100-300 mg of nickel nitrate, 200-600 mg of cobalt nitrate, 1-2 g of polyvinylpyrrolidone and 100-300 mg of trimesic acid, adding the materials into 30-60 mL of N, N-dimethylformamide, carrying out ultrasonic full dissolution, transferring the mixed solution into a reaction kettle, placing the reaction kettle into a 150 ℃ forced air drying box for carrying out solvent thermal reaction for 6 hours, carrying out centrifugal washing for multiple times by using absolute ethyl alcohol after the mixed solution is naturally cooled to room temperature, and finally drying the washed product;
(2) weighing 100-200 mg of the product centrifugally dried in the step (1) and 200-400 mg of melamine, respectively paving the product and the melamine in two ceramic boats, then placing the ceramic boats in a tubular furnace protected by argon and hydrogen for carbonization and nitrogen doping at the temperature of 450 ℃ for 2 h, and finally naturally cooling the ceramic boats to room temperature to obtain a nitrogen-doped carbon-coated nickel-cobalt double metal substance;
(3) and (3) weighing 30-60 mg of the product obtained in the step (2) and 150-300 mg of selenium powder, adding the product and the 150-0.4 mol/L hydrazine hydrate solution into the reaction kettle, transferring the reaction kettle into a 200 ℃ forced air drying box for 6 h solvothermal reaction, carrying out centrifugal washing for multiple times by absolute ethyl alcohol after the reaction kettle is naturally cooled to room temperature, and finally drying the washed product to obtain the nitrogen-doped carbon-coated two-phase staggered distribution type nickel-cobalt double-metal selenide electrode material.
3. The nitrogen-doped carbon-coated two-phase nickel-cobalt double metal selenide electrode material prepared by the preparation method of claim 1 or 2, wherein the nitrogen-doped carbon-coated two-phase nickel-cobalt double metal selenide electrode material comprises the following components in percentage by weight: the cobalt selenide and the nickel selenide are distributed in a staggered way, the organic ligand trimesic acid is carbonized to form carbon, and the nitrogen element in the melamine is doped into the carbon formed by the organic ligand trimesic acid in the carbonization and nitrogen doping treatment processes to form the nitrogen-doped carbon-coated two-phase nickel-cobalt double-metal selenide electrode material in a staggered way.
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